New indigoid dyestuffs



Patented Sept. 13, 1932 UNITED STATES PATENT OFFICE" RICHARD HERZ, OF FRANKFORT-QN-THE-MAIN, AND MAX SGHUBERTLAND BRUNNER, OF FRANKFORT-ON-THE-MAIN-FECHENHEIM, GERMANY, ASSIGNORS TO GENERAL ANILINE worms, 11m, OF

DELAWARE NEW YORK, 1v. 2., .A. CORPORATION OF riEw INDIGOIID nYEsrUEEs No Drawing. Application filed December 19, 1929, Serial ll'o. 415,352, and in Germany December 22, 1928.,

This invention relates to new valuable in- V In order to further illustrate our invention 15 of the general formula:

wherein the CH-group stands in the para position to the (JO-group and the benzene as well as the pyrazole nucleus may contain alkyl groups, which compounds are described in our copending U. S. application Serial No.

as 415,351, filed December 19, 1929, and a compound of the general formula:

wherein R and X are identified as above and Y means H 0, 01 or N-aryl. When using a compound wherein Y is H the condensation is effected in the presence of an oxidizing agent. The second component may be identical with the first one.

The new vat dyestuffs yield bluishrgrey to olive dyeings which show an excellent fastness to light and chlorine; the dyestuifs possess a remarkable levelling property. They 40, are distinguished by a likely good aflinity both to the vegetable and to the animal fiber, and in printing they are capable of being easily fixed on the fiber. Grey to olive vat dyestuffs for printing ofs'uch properties Were hitherto unknown.

the following examples are given, the parts being by weight and all temperatures in centigrade degrees. But we wish it to be understood that we are not limited to the particular conditions or specific products mentioned thereina" Example 1 30 parts of; the hydroxy-pyrazole-thionaphthene, described in Example l of our U. S. application Serial No. 415,351, filed December .19, 1929, which compound probably. 7

corresponds to one of the following formulae: /N o 0\ o o\ H/ HO \S/ CH2 01' CH2 are made into a paste by means of 100 parts of alcohol and dissolved with 200 parts of a solution of caustic soda of 4:70 strength.

Then an aqueous solution containing 10%of potassium ferri cyanide' are gradually added, or air is passed through the mixture,

until the precipitation of the dyestuffiscom or i oo oo q no \S/ on a I l\ /l It dissolves in concentrated sulfuric acid to a blue solution. Cotton is dyed from a brownish yellow hydrosulfite vat in 'cleargrey shades' i ,7

Example 2 When in Example 1 the hydroxy-pyrazolethionaphthene isreplaced by the equivalent amount of the hydroxy-methyl-pyrazolethionaphthene described in Example 3 of our U. S. applicationSerial No. 415,351, filed December 19, 1929, and the process is otherwise carried out in the same manner, a new dyestuff is obtained which corresponds probably to the formula:

mo CH3 A oo oo I no i s/ I an act Nae- It represents-when dry: a black powder, sol

uble in concentrated sulfuric acid with a blue tint dyeing cotton from a brownish-yellow hydrosulfite vat clear grey shades.

r Ewemple a hen N-methyl-hydroxy pyr'az olethioo naphthene, described in Example2of-our U. S. application Serial No. 415,351, filed December 19, 1929, which compound probably corresponds toone of the formulae:

is subjected to theprocess of Example 1, a dyestuif is; obtained which probably, corresponds to one of the formulae:

thene used in Example 1 are dissolved in 800 parts of hot glacial acetic acid. The-solu tion is poured into a solution of parts of 3-hydroxy-5.6-benzo-thi0naphthene-2-anil in 800 parts of glacial acetic acid. After the addition of parts oat anhydrous sodium acetate the mass is warmed for half an hour in a boiling water-bath. The dyestufi which has precipitated from the cold mass is filtered, washed with glacial acetic acid and with water and dried. It probably corresponds to one of the formulae: I o I r It represents a-bluish-blaek powder, soluble j in concentrated'sulfuric acid with a bluish green tint, dyeing cotton from a brownishyellow hydrosulfite Vatbluish-greyshades.

Example 5 i .80 parts of 5-chloro-isatine are heated with 300 parts ofv mono-chloroebenzene and 35 parts of phosphorus penta-chloride ina salt water bath for 1 2'hours at" about 110.

To the clear solution thus obtained a hot solu- 7 tion of 26 parts of hydroxy-pyrazole-thionaphthene used inExample 1 and 300 parts of mono-chloro-benzene are added, and the mass is warmed for about half an hour in the boiling Water bath. The'dyestufi which has precipitated is filtered oil, Washed with monochloro-benzene and dried." 1

The new dyestufiprobably corresponds to one of theformulae: i

It representsa dark blue powder, soluble in concentrated sulfuric acid with a blue tintand dyes cotton from a'yellow hydrosulfite vat bluish-grey shades.

I 7 Example 6 I A mixture of the hydroxy-pyrazole-thionaphtheneused rinExaInple' 1 and of 4.5-.

benz isatine-Z-chloride is heated With'nitrobenzene .to 150. From thecold mass the dyestutf which has precipitatedais filtered, 1'3

, washed and dried. it probably corresponds to one of the formulae:

It dyes cotton olive green shades of a very good fastness and is distinguished by an excellent capacity of being fixed.

Example 7 When the same hydroxy-pyrazole-thiodensed with 6.7-benzo-3-hydroxy-thionaphthene-Q-anil in the presence of glacial acetic acid, a new dyestulf is obtained which probably corresponds to one of the formulae:

and dyes cotton fast grey shades.

We claim: '1. As newcompounds the indigoid dyestuffs corresponding probably to the general formula:

N CO CO war M R wherein the -S-atom and the -CO-group in the thiophene ring are attached to ortho-carbons of the benzene nucleus and the OH- group stands in the para position to the CO-group, the benzene as well asthe pyrazole nucleus may contain alkyl groups, R means an aromatic residue and X means NH or S, which compounds are when dry colored powders, dyeing cotton bluishgrey to olive shades of an excellent fastness to light and chlorine and of a remarkable levelling property, having a likely good af- C5 finity both for vegetable and animal fiber,

naphthene as used in the Example 1 is conand being'capable of being easily fixed on the fiber when used for printing cotton.

"2. "Asa new compound the indigoid dye stufi' probably corresponding to one'ofthe formulae r 'oo 7 I oo nr 110 s \NH which compound is when dry a dark colored powder, dyeing cotton olive green shades of an excellent fastness to light and chlorine and of a remarkable levelling property, having a likely good afiinity both for vegetable and animal fiber, and being capable of being easily fixed on the fiber when used for printing cotton.

3. As a new compound the indigoid dyestufl' probably corresponding to one of the formulae V o o o o which compound is when dry a black powder dyeing cotton from abrownish-yellow hydrosulfite vat clear grey shades of an excellent fastness to light and chlorine and of a re markable levelling property, having an equally. good aflinity for both vegetable and animal fiber, and being capable of being easily fixed on the fiberwhen used for printing cotton. 7

4. As a new compound the indigoid dyestuif probably corresponding to the formula:

which compound is when dry a black powder dyeing cotton from a brownish-yellow equally good afiinit y for both vegetable and animal fiber, and being capable: .of being easily fixed on the fiberv when used. fqrpripting cotton.

2 5 In test 1mony whreqflwe aifiiz OunsighaE tures.

' RICHARD HERZ.

MAX SCHUBERT. WALTERBRUNNER. 1 

